Carrying out friedel crafts and similar condensation reactions with nonaromatic compounds



enema Feb. 28,1933

UNITED STATES Puma-ms KERHANN m1: AND HAmED pom OIFEARN'EEII, AND ERNST OI" LUDwIGSEAFEN-ON-TEE-BHINE, GERMANY, ABSIGNOBS TO I. G, IABIBENINDUBTBIE AKTIENGESELLSCEAIT, OI rmxron'r-oN-m-m, 61:11am, A. (DBPOBA'II OH OI GERMANY GABBYDTG OUT IBEDEL Io Drawing. Application fled Iebmry 88, 1929,

Hitherto the Friedel crafts and similar condensation reactions could only be carried out with compounds of the aromatic series.

We have now found that aliphatic hydro-' aromatic or aromatic radicals can be introduced with ood results into saturated cornpounds of t e aliphatic, namely of the ah-- hatic open chain and hydroaromatic series, ree from halogen, by treating the said compounds with compounds of the aliphatic, hydroaromatic or aromatic series containing 7 mixture. The valve of the pressure de nds on the reaction components emplo e and varies accordingly from about 2 to a out atmospheres depending on the temperature substituents of the aforesaid nature which hitherto could only be introduced into substances of the aromatic series can be introduced into saturated aliphatic com ounds free jgom halogen already mentione such as aliphatic or hydroaromatic com ounds,

by means of l halides, halides of monoor polybasic aci s and the like with the aid of the more or less volatile meta-l halides such as aluminium chloride or bromide, iron chloride and the like. The process can also be carried out in the presence of diluents cyclo polymetllligenes, ethers and t e like,

which are not attacked such as carbon tetrachloride, chloroform or similar substances containin halogens which themselves cull-my permit 0 further halogenation with d' culti inventionis not restricted to these examples. The parts are by weight.

Example 1 norunomrrc' conroonns v A is further examples will further illustrate the nature of the said invention but the can as m suntan connnnsarr'on anemone wrni term in. 343,550, and in arm, mien 5, 1m.

conversion into ketones of the polymethylene and parafiin series occurs. I

Ewamiplel? v A strongly cooled autoclave is charged,

-with n-butane and thedouble compound of pho ene .and aluminium chloride. It is then eated to 90 centigrade and kept at this temperature for'6 hours. After cooling, the

pressure is released and the reaction mixture Q is worked up in the' usual manner. A yellow oil with an aromatic smell is obtained which boils' between and oentigrade at 15 millimetres pressure (mercury gauge).

Example 3 i 7 8 parts of acet lchloride and 100 parts of hexane (e. g. wit a sli ht excess above the quantity stolchiometrica 1y required) are fed into an autoclave to ether with the amount of aluminium chlori e calculated for the for- -mation of itsdouble compounds with the acetylchlorid'eand then heated for 2 hours to 100 C. The product obtained consists mainly of ketones of the polymethylene series,

inter alia octanone.

ampze 40 parts of ethyl chloride and 100 parts of hexane are heated in an autoclave together with the calculatedquantity of aluminium chloride for 2 hours at 100 C. -The reaction product is worked up in the usual manner and higher h drocarbons, particularly octane, can be iso ated therefrom.

What we claim is 1 y 1. The process of carrying out condensationreactions with non-aromatic com ounds which comprises treating an aliphatic saturated hydrocarbon with a halogenated oxygen-bearing organic compound in the presence of a volatile metal halide in a closed vessel and at a temperature above the boiling point'at atmospheric pressure of the non- -aromatic ingredient of the reaction mixture but below the temperature. at which the reaction components are cracked.

2. The rocess of carrying out condensation reactions with non-aromatic compounds which comprises treating an aliphatic eaturated hydrocarbon with a halogenated oxygen-bearing organic com ound in the presence of aluminium chlori e in a closed vessel and at a temperature above the boil- 5 ing point at atmospheric ressure of flie nonaromatic ingredient of t e reaction mixture but below the temperature at which the reaction components are cracked;

3. The process of carrying out condensa- 19 tion reactions with non-aromatic com ounds which comprises reating a mineral 011 fraction consisting of saturated constituents with a halogenated oxygen-gearin organic compound in the presence of a uminium chloride in a closed vessel and at a temperature above the boiling point at atmospheric pressure of the mineral oil fraction but be,

low the temperature at which the reaction components are cracked.

4. The process of carrying out condensationreactions with non-aromatic compounds which comprises treating a mineral oil-fraction consisting of saturated constituents with phosgene in the presence of aluminium E5 chloride in a closed vessel and at a temperature above the boiling point at atmospheric ressure of the mineral oil fraction but beow the temperature at which the reaction components are cracked.

E3 5. The process for carrying out condensation reactions with non-aromatic compounds which comprises treating a petroleum fraction boiling between and C., with phosgene in the presence of aluminium chloride in a closed vessel, at a temperature of about 100 C.

6. The process forcarrying out condensation reactions with non-aromatic compounds which comprises treating n-butane with F? phosgene in the presence of aluminium chloride in a closed vessel at a temperature of about C.

7. The process for carrying out condensation reactions with non-aromatic compounds 5 which comprises treating hexane with acetyl chloride in the presence of aluminium chloride in a closed vessel, at a temperature of about C. I 1

8. The process for carrying out condensa- 53 tion reactions with non-aromatic compounds which comprises treating hexane with .ethyl chloride in the presence of "aluminium chloride in a closed vessel at a temperature of about 100 C.

5 In testimony whereof we have hereunto set our hands.

HERMANN MARK. MANFRED DUNKEL. ERNST ROELL. 

